This study investigates the translational and rovibrational energy of vacuum-ultraviolet (VUV) photodesorbed CO molecules from a CO polycrystalline ice (15 K) at ∼8 eV. The electronic excitation was produced by a pulsed VUV laser, and the photodesorption of CO molecules in their ground and first vibrational states was observed using resonance enhanced multiphoton ionization. Time-of-flight and rotationally resolved spectra were measured, and the kinetic and internal energy distribution were obtained. Vibrationally cold CO molecules were observed, with little energy in rotation and translation (≤300 meV). Ab Initio Molecular Dynamics (AIMD) simulations focusing on the description of the vibrational energy redistribution within an aggregate of 50 CO molecules were performed. The measured energy distributions are in very good agreement with those predicted by AIMD simulations. The rotational energy was found to slightly increase with translational energy, a trend also predicted by theory. This confirms the validity of the indirect desorption mechanism triggered by the excitation of CO in a high vibrational state.
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